Treatment of gasolines



Patented Sept. 29, 1942 UNITED STATES PATENT OFFICE TREATMENT OF GASOLINES Ralph B. Thompson, Chicagm llL, assignor to Universal Oil Products Company, Chicago, 111., a corporation of Delaware No Drawing. Application June 24, 1940,

Serial N0. 342,125

23 Claims. (01. 44-69) This invention'relates to a method for preventing the deterioration of gasolines when exposed to sunlight. More particularly it relates to preventing depreciation of gasolines containing tetraethyl lead when exposed to light. 1

Due to. the fact thatmotor fuels are often dispensed from pumps having glass bowls in which the gasoline is contained and which may be exposed to sunlight for indefinite periods of time, it becomes necessary to treat certain gasolines to prevent depreciation of color and other properties such as antiknock value of the gasolines so exposed. Many motor fuels tend to become hazy or cloudy upon exposure to sunlight and this is particularly true of gasolines contalning tetiaeth'yl lead which has been added to improve the octane number of the motor fuel. The use of certain compounds, particularly alkyl amines, to prevent such cloudiness in gasolines containing no tetraethyl lead has been practiced. These compounds alone, however, are not particularly effective in preventing haze formation in leaded gasolines. The present invention relates to a method for. preventing such haze formation together with the consequentloss' in antiknock value, resulting from prolonged exposure to sunlight.

In one specific embodiment the present invention comprises a method for preventing haze formationin motor fuel by adding theretoa relatively minor amount of an alkyl amine salt 01 an organic ester of an acid of phosphorus.

Several types of such salts may exist and these may be represented by the following structural formulae:

Lo-i R in the above formulae represents an organic group such as an alkyl group, or in some cases an aromatic group. The various groups -need not be the same in all cases. The group designated (NR/a) represents an alkylamine.

These may include mono-, dior trialkylamines.

exactly equivalent in their action and should not be so interpreted.

The quantity of the amine salt of the organic phosphate which is necessary to protect the gasoline against haze formation is usually within the limits of approximately 0.005-0.05% by weight of Y the gasoline, although larger or smaller amounts may be. necessary in certain instances. The

compounds of the invention are readily soluble in gasoline and may be added directly thereto or may be first dissolved in a portion of the gasoline to form a concentrated solution which may then be injected into the gasoline as desired. The compounds are added to the gasoline after other forms of treatment such as acid-treating, sweetening, clay treating, etc., have been carried out and the gasoline is ready'to be stored prior to use. These compounds are effective in gasolines containing no tetra-ethyl leadand prevent color depreciation and haze formation therein. Their greatest utility is, however, in gesolines containing added tetraethyl lead, since exposure to strong light of such gasolines without the compounds of this invention being added, leads to haze forvania straight-run and cracked gasolines containing 3 cc. of tetraethyl lead per gallon and to which 0.05%v ofthe indicated salts had been added. The gasoline was then exposed in fourounce fused quartz bottles to'the light of a carbon arc lamp. The samples were examined at intervals of about two minutesand the length of time at which the appearance of. haze was first noted was recorded. 1 The carbon arc lamp test is comparable to tests in natural sunlight with the exception that the amount of ultraviolet In cases where dior triamines are used, the alkyl, radiation is greatly concentrated so that the arc of this invention compared with the gasolines containing no added compound.

' Haze g5? time Inhibitor min. in ig Pa. crkd 88$ gasoline Dune Di-tolyl lihosphate-wctyl amine 12 19 Di- -amy phosphate-octyl amine- 22 z; Octyl acid pyrophosphate-octyl amine, normal salt 20 31 :3: acid pyrophosphato-octyl amine, acid 28 16 i-Am1"wt ""i' fi""1ie-oc""'51 am 1 'n'IIIIIIIII i 28 19 i-Amyl aci pyr g osphawoctyl amine, nor- 11181 ML. 25 53 i-Amyl acid pyrophosphate-octyi amine, acid 32 20 n-But' 'i i iiiir'iiilifiiik'te 'tyi 5115591111111 31 3a Di-tolyl phosphatr-octadecyl amine 17 21 Di-i-amyl phosphate-octadecyl amine 24 60 Octyl acid yrophosphata octadecyl amine,

oi -d am 1 n am 0 y e acid c.3222? 4s 20 i-Amyloctyl phosphate-octadecyl amine. 25 52 i-Amyl acid pyrophosphate-octadecyl amin normal saith. i-Awimglzlcid pyrophosphate-oetadecyl amine, ii-num-i-iifi' 'i'iiiffifikw-oc Eli 669i am i n 3.1".

Di-tolyl phosphatedioctyl amine Di-i-amyl phosphate-dicotyl amine Orr-till pyrophosphate-dioctyl amine, nor- Octyl ac 'd'iiiifiifiifi 'di'o't'ii ac i-Amyl'otylpliosphate-diocWl amine i-Amyl acid pyrophosphate-dioctyl amine,

normal salt i-Amyl acid pyrophosp te-dioctyl amine,

acid salt n-Butyl-i-amyl phosphate-dicotyl amine- Di-toiyl phosphatetriamylamine Di-i-Amyl phosphate-triamylamine Octyl v acimgil pyrophosphatetnam' ylamine,

normal Octyl acid pyrophosphate-trlamylainine,

acid t i-Amyloctyl hosphate-trlamylamine i-Amyl sci pyrophoephate-triamylamine,

normal salt 4i i-Anligl acid pyrophosphate-triamylamine, 36

ac n-Butyl-i-amyl phosphate-trlamylamine 12 'Rlnn'k 9 16 I claim as my invention: 4

l. A process for preventing color depreciation of gasolines exposed to light which comprises adding thereto a relatively minor amount of an alkylamine salt of an organic phosphate, the organic component of said phosphate being a hydrocarbon radical consisting of carbon and hydrogen. 4

2. A process for preventing color depreciation in gasolines upon exposure to sunlight which comprises adding theretov an amine salt of an organic ester of an acid of phosphorus having the following general structure:

wherein R is an organic radical and (NR':) is an alkylamineu g 3. A process for preventing color depreciation organic ester of an acid of phosphorus having the following general structure:

' R-O 0 0 OR \II II/ P-O -P (R'aN).HO OH wherein R is an organic radical and (R'aN) is an prises adding to said gasolines an amine salt of in gasolines upon exposure to sunlight which comprises adding thereto an amine salt of an an organic phosphate, the organic component of said phosphate being a hydrocarbon radical consisting of carbon and hydrogen.

6. A process for preventing haze formation in sunlight of gasolines containing tetraethyl lead which comprises adding thereto an alkylamine salt of an organic ester of an acid of phosphorus having the following general structure:

R-O 0H.(NR)

wherein R is an alkyl group and (NB/s) is an alkylamine. a

7. A process for preventing haze formation in sunlight of gasolines containing tetraethyl lead which comprises adding thereto an alkylamine saltv of an organic ester of an acid of phosphorus having the following general structure:

R-O o 0 on t ammo on wherein R is an alkyl group and (NR/3) is an alkylamine.

8. A process for preventing haze formation in sunlight of gasolines containing tetraethyl lead which comprises adding thereto an allwlamine salt of an organic ester of an acid of phosphorus having the following general structure:

\II ll/- /P0--P\ mmaio 011mm) wherein R is an alkyl group and (R'sN) and (NR/a) are alkylamines.

9. An inhibitor for preventing haze format on in gasolines exposed to sunlight comprising essentially an alkylamine salt of an organic phosphate, the organic component of said phosphate being a hydrocarbon radical consisting of carbon and hydrogen. I 4

10. An inhibitor useful for preventing haze formation in sunlight of gasolines con g tetraethyl lead comprising essentially an alkylamine salt of an organic phosphate, the organic component of said phosphate being a-hydrocarbon radical consisting of carbon and hydrogen.

11. An inhibitor useful for preventing haze formation insunlight oi gasolines containing 11-0 011. (N R's) wherein R'is an alkyl group and (R'aN) is an alkylamine.

13. An inhibitor useful for preventing haze formation in sunlight of gasolines containing tetraethyl lead which comprises essentially an amine salt of an organic ester of an acid of phosphorus having the general structure:

(RaN).H0 011mm) wherein R is an alkyl group and (R'aN) and (NR'a) are allwlamines.

14. The process of claim 1 wherein the compound is added in concentration within the limits of approximately 0.005 to 0.05% by weight of the gasoline.

15. A method for stabilizing atom... normally tending to form haze upon exposure to sunlight,

which comprises adding to the gasoline an alkylamine saltoi an organic phosphate in sufficient amount to substantially prevent haze formation in the gasoline, the organic component of said phosphate being a hydrocarbon radical consisting of carbon and hydrogen.

16. Motor fuel comprising gasoline normally tending to form haze on exposure to sunlight and an alkylamine salt of an organic phosphate in suflicient amount to. substantially prevent haze formation in the gasoline, the organic component of said phosphate being a hydrocarbon radical consisting of carbon and hydrogen.

17. Gasoline containing a minor quantity ofv lead tetraethyl which normally tends to decompose in storage, and as a stabilizer therefor, a small quantity of an alkyl amine salt of an alkyl pyrophosphoric acid ester.

18. The method as defined in claim 15 further characterized in that said organic phosphate is an ester of pyrophosphoric acid.

19. The method as defined in claim 15 further characterized in that said hydrocarbon radical is an alkyl group.

20. The method as defined in claim 15 further characterized in that said hydrocarbon radical is an alkyl group.

23. Motor fuel as defined in claim 16 further characterized in that said hydrocarbon radical is an aryl group.

RALPH B. THOMPSON. 

